Photo-generated high-energy surface states can help to produce chlorine in aqueous environments. Here, aligned rutile (TiO2) nanocrystal arrays are grown onto fluorine-doped tin oxide (FTO) substrates and activated either by hydrothermal Sr/Ba surface doping and/or by vacuum-annealing. With vacuum-annealing, highly photo-active films are obtained with photocurrents of typically 8 mA cm-2 at 1.0 V vs. SCE in 1 M KCl (LED illumination with = 385 nm and approx. 100 mW cm-2). Photoelectrochemical chlorine production is demonstrated in proof-of-concept scale in 4 M NaCl and suggested to be linked mainly to the production of Ti(III) surface species by vacuum-annealing, as detected by XPS, rather than to Sr/Ba doping at the rutile surface. The vacuum-annealing treatment is proposed to beneficially affect (i) bulk semiconductor TiO2 nanocrystal properties and electron harvesting, (ii) surface TiO2 reactivity towards chloride adsorption and oxidation, and (iii) FTO substrate performance.
|Publication status||Acceptance date - 26 Oct 2020|